PORPHYRIN SYNTHETIC METHODS FOR BIOORGANIC APPLICATIONS

用于生物有机应用的卟啉合成方法

• 批准号: 3289794
• 负责人: JONATHAN SIDNEY LINDSEY
• 金额: $ 16.87万
• 依托单位: CARNEGIE-MELLON UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1986
• 资助国家: 美国
• 起止时间: 1986-12-01 至 1995-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3289794
• 关键词: aldehydes; chemical models; chemical structure function; chemical substitution; chemical synthesis; chlorin; cytochromes; ferrocene; lipid bilayer membrane; molecular asymmetry; molecular shape; oxidation reduction reaction; oxidizing agents; photochemistry; porphyrin biosynthesis

Our long-term objectives are to develop synthetic methods for creating bioorganic molecules which can be used to provide insight into the relation between molecular structure and biological function. We have developed a room temperature biomimetic synthesis of tetraphenyl-porphyrin in 60% yield. We will expand the scope of this methodology to prepare porphyrins which have previously been unobtainable. This includes the class of meso-alkylporphyrins, some of which should be extremely soluble in lipid media. Amphipathic porphyrins can then be prepared for bilayer studies. Then we will exploit this new methodology in the high yield synthesis of cofacial dimers containing porphyrins and chlorins. We plan an extensive study of the electronic interactions resulting from the juxtaposition of rings. To model the light harvesting apparatus of photosynthesis, we will design and synthesize porphyrins bearing bulky substituents which in the crystalline state will hold the porphyrins at fixed distances apart. Fluorescence measurements in applied electric fields should provide data to distinguish the mechanisms of energy transfer. These new synthetic porphyrins should be of considerable value in extending our understanding of the properties of heme and chlorophyll in biological systems. A more global problem in bioorganic chemistry is the synthesis of model systems having well-defined 3-dimensional structures. We propose to create modular model systems of the photosynthetic process which contain a donor and acceptor covalently linked in a stacked geometry. The spacer groups separating the donor and acceptor are composed of p-aminobenzoic subunits, which are coupled together in a stepwise manner analogous to peptide and DNA synthesis. Three porphyrin-quinone compounds of 5, 10, and 15 A separation will be prepared which have 1, 2, and 3 subunits in their spacer groups. The photochemical characterization of this family of molecules will provide a systematic study of the effect of distances on electron transfer reactions. This modular approach should have broad applicability in the bioorganic field.

我们的长期目标是开发合成方法来创造 生物有机分子可以用来洞察这种关系 分子结构和生物功能之间的关系。 我们开发了一种室温仿生合成 四苯基卟啉，产率60%。我们将扩大这一范围 制备以前无法获得的卟啉的方法学。 这包括中位烷基卟啉类，其中一些应该是 在脂类介质中极易溶解。然后两亲性的卟啉就可以 为双层研究做好准备。然后我们将利用这种新的方法在 高产率合成含二茂铁衍生物的界面二聚体 绿素。我们计划对电子相互作用进行广泛的研究 由于环的并置而产生的。对采光过程进行建模 光合作用装置，我们将设计和合成卟啉 含有大体积取代基的，这些取代基在结晶状态下将保持 以固定的距离分开的卟啉。应用中的荧光测量 电场应该提供数据来区分能量的机制 调职。这些新合成的卟啉应该有相当大的价值。 在扩大我们对血红素和叶绿素性质的理解中 生物系统。 生物有机化学中一个更具全球性的问题是模型的合成 具有明确定义的三维结构的系统。我们建议创建 含有供体的光合作用过程的模块化模型系统 和受主共价连接成堆积几何结构。间隔基 分离的供体和受体由对氨基苯甲酸亚基组成， 它们以类似于肽的逐步方式连接在一起，并且 DNA合成。3种5，10和15A的卟啉-苯二酮化合物 将制备在其间隔物中具有1、2和3个亚基的分离 组。这类分子的光化学特征 将对距离对电子的影响进行系统的研究 转移反应。这种模块化方法应该具有广泛的适用性 在生物有机领域。